Azo dye from diphenyloxide derivatives



Patented Aug. 16, 1932 UNITED STATES PA'TENQ oFFwE ERNEST F. GRETHER, OF .MIDLAND, MICHIGAN, ASSIGNOR THE DOW CHEMICAL COMPANY, OF MIDLAND, MICT-IIGAN, A CORPORATION OF MICHIGAN .AZO DYE FROM DIPHENYLOXIDE DERIVATIVES No Drawing.

The present invention relatesto azo dyes of direct-developed type prepared by coupling a diazotized halogenated amino-diphenyloxide with a hydroxynaphthoic acid arylide.

It is known that azo dyes which are water insoluble and fast to light and washing may be produced by coupling diazo or tetrazo components into arylides of 2.3-hydroxynaphthoic acid. I have now discovered new and useful dyes of direct-developed type which may be prepared by diazotizing a halogenated amino-diphenyloxideand coupling therewith a suitable hydroxy component of the above mentioned type. Such dyes, which are very fast to light, bleach, and washing, may be represented by the following general formula, V

wherein X represents a halo group, and R a residue of a primary aromatic amine.

My invention, then, consists of the steps and new dyes hereinafter fully described and .iu particularly pointed out in the claims, the

following description setting forth but several ways in which the principle of the inven tion may be used. The herein described azo dyes, which dye as cotton and other fibers directly in fast and clear shades, may be prepared by coupling one of the above mentioned amines, such as 4- amino-Q-chloro-diphenyloxide or the corre- V spending bromo compound, into suitable hyeu droxynapht-hoic acid arylides in any of the ordinary ways. F or instance, the dyes may be applied by developing on the fibeiyby printing a diazo solution upon padded goods, by using nitrosamine salts of the corresponding bases, or may be prepared in substance for use as in pigments. Mordanting or otherauxiliary treatment for promoting the absorption of the dye onthefiber,orafter-treatmentwith metallic salts such as chromium, copper, or aluminum salts, for fixing the dye or modify- 7 Application filed February 2, 1931. -Serial. No."513,056.-

ingits color tone, may be optionally employed in conjunction with the dyeing operation, the present invention-being intended to include not only the dyes but also material dyed therewith; v

' The following specific example illustrates various ways inwhich my invention may be carrled out. V V V f Emamplel Cotton fiberswere impregnated with an aqueous alkaline solution of 2.3-hydroxynaphthoyl aniline, then rinsed in water and immersed in a dilute aqueous sodium carbonate solution to which had been added a diazo solution prepared from t-amino-Q- chloroediphenyloxidet The dye developed on the fiber, having a scarlet color and the formula,

.As described fin the above, example, the same diazo component was coupled into other arylides, as represented 'in, the following table z I 7 I 2.3-hydroxynaphthoic acid arylide of Color of. dye

3-nitl'oani linp- Carmine 3.4-dichloroani1ine Castilian red 3-amino-a-methoxy diphenyl; 'Castilian red Lamino-naphthalene Goya 2-methy1aniline Scarlet 4.4-diamino-diphenyloxicle (di-arylide) Dark scarlet WVhile cottom fibers have been mentioned in the example as the material to be dyed with the new azo dyes of my present invention, other natural or synthetic fibers may likewise be dyed therewith, e. g. wool, silk, rayon, andthelike.

In brief, my invention concerns azo dyes produced by combining a diazo component having the general formula,

wherein X represents a halo group, and wherein the benzene nuclei may carry other substituent groups such as halo, alkyl, nitro, or ether groups, with an arylide of a hydroxynaphthoic acid, such arylide type being intended to include bisand poly-arylides.

Other modes of applying the principle of my invention maybe employed instead of the one explained, change being made as regards,

the steps or materials employed, provided the details stated by any of the following claims or the equivalent thereofbe employed.

I therefore particularly point out and distinctly claim as my invention 1. The method of making an azo dye, which comprises coupling a diazotized t-amino-2-halo-diphenyloxide with an arylide of a hydroxynaphthoic acid.

2. The method of making an azo dye, which comprises coupling a diazotized 4'-amino-2-chloro-diphenyloxide with an arylide of a hydroxynaphthoic acid. 7

3. The method of making an azo dye, which comprises coupling a diazotized 4-amino-2-halo-diphenyloxide with an arylide of 2.3-hydroxynaphthoic acid.

4. The method of making an azo dye, which comprises coupling a di'az'otized lt-amino-2-chloro-diphenyloxide with an arylide 0f 2.3-hydroxynaphthoic acid. I

5. The method of making an azo dye,

which comprises coupling a diazotized 4- amino-2-chloro-diphenyloxide with a bisarylide of 2.3-hydroxynaphthoic acid.

6. As a new compound, an azo dye prepared by coupling a l-amino-2-halo-diphenyloxide with an arylide of a hydroxynaphthoic acid.

7 As a new compound, an azo dye prepared by coupling a t-amino-Q-chloro-diphenyloxide with an arylide of a hydroxynaphthoic acid.

8. As a new compound, an azo dye prepared by coupling a 4.-amino-2-halo-di-- phenyloxide with an arylide of a 2.3-hy droxynaphthoic acid.

9. As a new compound, an azo dye pre- 7 the following formula,

oom1-n wherein R represents a residue of a primary aromatic amino. 12. As a new compound, an azo dye having the following formula,

OH HO- Signed by me this 12 day of January, 1931.

. ERNEST F. GRETHER. 

